Silicon particles for battery electrodes

ABSTRACT

Silicon particles for active materials and electro-chemical cells are provided. The active materials comprising silicon particles described herein can be utilized as an electrode material for a battery. In certain embodiments, the composite material includes greater than 0% and less than about 90% by weight of silicon particles. The silicon particles have an average particle size between about 0.1 μm and about 30 μm and a surface including nanometer-sized features. The composite material also includes greater than 0% and less than about 90% by weight of one or more types of carbon phases. At least one of the one or more types of carbon phases is a substantially continuous phase.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a continuation of U.S. application Ser. No.17/540,399, filed Dec. 2, 2021, which is a continuation of U.S.application Ser. No. 16/821,072, filed Mar. 17, 2020, which is acontinuation of U.S. application Ser. No. 15/413,021, filed Jan. 23,2017, which is a continuation of U.S. application Ser. No. 13/799,405,filed Mar. 13, 2013, which is a continuation-in-part of U.S. applicationSer. No. 13/601,976, filed Aug. 31, 2012, which claims the benefit ofU.S. Provisional Application No. 61/530,881, filed Sep. 2, 2011 and isalso a continuation-in-part of U.S. application Ser. No. 13/008,800,filed Jan. 18, 2011, which claims the benefit of U.S. ProvisionalApplication No. 61/295,993, filed Jan. 18, 2010 and also claims thebenefit of U.S. Provisional Application No. 61/315,845, filed Mar. 19,2010, the disclosures of each of the above referenced applications arehereby incorporated by reference in their entirety.

BACKGROUND Field

The present application relates generally to silicon particles. Inparticular, the present application relates to silicon particles andcomposite materials including silicon particles for use in batteryelectrodes.

Description of the Related Art

A lithium ion battery typically includes a separator and/or electrolytebetween an anode and a cathode. In one class of batteries, theseparator, cathode and anode materials are individually formed intosheets or films. Sheets of the cathode, separator and anode aresubsequently stacked or rolled with the separator separating the cathodeand anode (e.g., electrodes) to form the battery. Typical electrodesinclude electro-chemically active material layers on electricallyconductive metals (e.g., aluminum and copper). Films can be rolled orcut into pieces which are then layered into stacks. The stacks are ofalternating electro-chemically active materials with the separatorbetween them.

SUMMARY

One embodiment provides silicon particles for use in an electrode in anelectro-chemical cell comprising an average particle size between about10 nm and about 40 μm.

One embodiment provides an electrode for use in an electro-chemical cellcomprising silicon particles, the silicon particles having an averageparticle size between about 10 nm and about 40 μm.

Another embodiment provides an electro-chemically active materialcomprising silicon particles, the silicon particles having an averageparticle size between about 10 nm and about 40 μm.

Another embodiment provides a composite material comprising: greaterthan 0% and less than about 90% by weight silicon particles, the siliconparticles having an average particle size between about 10 nm and about40 μm; and greater than 0% and less than about 90% by weight of one ormore types of carbon phases, wherein at least one of the one or moretypes of carbon phases is a substantially continuous phase.

Another embodiment provides a composite material comprising: greaterthan 0% and less than about 90% by weight of silicon particles, thesilicon particles having an average particle size between about 0.1 μmand about 30 μm and a surface comprising nanometer-sized features; andgreater than 0% and less than about 90% by weight of one or more typesof carbon phases, wherein at least one of the one or more types ofcarbon phases is a substantially continuous phase.

Another embodiment provides an electrode configured to be used in anelectro-chemical cell. The electrode comprises an average particle sizebetween about 0.1 μm and about 30 μm; and a surface comprisingnanometer-sized features disposed thereon.

A further embodiment provides a method of forming a composite material.The method comprises providing a plurality of silicon particles havingan average particle size between about 0.1 μm and about 30 μm and asurface comprising nanometer-sized features; forming a mixturecomprising a precursor and the plurality of silicon particles; andpyrolysing the precursor to convert the precursor into one or more typesof carbon phases to form the composite material. In some suchembodiments, providing a plurality of silicon particles comprisesproviding silicon material; and synthesizing the silicon material toform the plurality of silicon particles comprising an average particlesize between about 0.1 μm and about 30 μm and a surface comprising thenanometer-sized features.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 illustrates an embodiment of a method of forming a compositematerial that includes forming a mixture that includes a precursor,casting the mixture, drying the mixture, curing the mixture, andpyrolysing the precursor;

FIGS. 2A and 2B are SEM micrographs of one embodiment of micron-sizedsilicon particles milled-down from larger silicon particles.

FIGS. 2C and 2D are SEM micrographs of one embodiment of micron-sizedsilicon particles with nanometer-sized features on the surface.

FIG. 3 illustrates an example embodiment of a method of forming acomposite material.

FIG. 4 is a plot of the discharge capacity at an average rate of C/2.6;

FIG. 5 is a plot of the discharge capacity at an average rate of C/3;

FIG. 6 is a plot of the discharge capacity at an average rate of C/3.3;

FIG. 7 is a plot of the discharge capacity at an average rate of C/5;

FIG. 8 is a plot of the discharge capacity at an average rate of C/9;

FIG. 9 is a plot of the discharge capacity;

FIG. 10 is a plot of the discharge capacity at an average rate of C/9;

FIGS. 11A and 11B are plots of the reversible and irreversible capacityas a function of the various weight percentage of PI derived carbon from2611c and graphite particles for a fixed percentage of 20 wt. % Si;

FIG. 12 is a plot of the first cycle discharge capacity as a function ofweight percentage of carbon;

FIG. 13 is a plot of the reversible (discharge) and irreversiblecapacity as a function of pyrolysis temperature;

FIG. 14 is a photograph of a 4.3 cm×4.3 cm composite anode film withouta metal foil support layer;

FIG. 15 is a scanning electron microscope (SEM) micrograph of acomposite anode film before being cycled (the out-of-focus portion is abottom portion of the anode and the portion that is in focus is acleaved edge of the composite film);

FIG. 16 is another SEM micrograph of a composite anode film before beingcycled;

FIG. 17 is a SEM micrograph of a composite anode film after being cycled10 cycles;

FIG. 18 is another SEM micrograph of a composite anode film after beingcycled 10 cycles;

FIG. 19 is a SEM micrograph of a composite anode film after being cycled300 cycles; and

FIG. 20 includes SEM micrographs of cross-sections of composite anodefilms.

FIG. 21 is an x-ray powder diffraction (XRD) graph of the sample siliconparticles.

FIG. 22 is a SEM micrographs of one embodiment of silicon particles.

FIG. 23 is another SEM micrographs of one embodiment of siliconparticles.

FIG. 24 is a SEM micrographs of one embodiment of silicon particles.

FIG. 25 is a SEM micrographs of one embodiment of silicon particles.

FIG. 26 is a chemical analysis of the sample silicon particles.

FIGS. 27A and 27B are example particle size histograms of twomicron-sized silicon particles with nanometer-sized features.

FIG. 28 is a plot of discharge capacity during cell cycling comparingtwo types of example silicon particles.

DETAILED DESCRIPTION

Typical carbon anode electrodes include a current collector such as acopper sheet. Carbon is deposited onto the collector along with aninactive binder material. Carbon is often used because it has excellentelectrochemical properties and is also electrically conductive. If thecurrent collector layer (e.g., copper layer) was removed, the carbonwould likely be unable to mechanically support itself. Therefore,conventional electrodes require a support structure such as thecollector to be able to function as an electrode. The electrode (e.g.,anode or cathode) compositions described in this application can produceelectrodes that are self-supported. The need for a metal foil currentcollector is eliminated or minimized because conductive carbonizedpolymer is used for current collection in the anode structure as well asfor mechanical support. In typical applications for the mobile industry,a metal current collector is typically added to ensure sufficient rateperformance. The carbonized polymer can form a substantially continuousconductive carbon phase in the entire electrode as opposed toparticulate carbon suspended in a non-conductive binder in one class ofconventional lithium-ion battery electrodes. Advantages of a carboncomposite blend that utilizes a carbonized polymer can include, forexample, 1) higher capacity, 2) enhanced overcharge/dischargeprotection, 3) lower irreversible capacity due to the elimination (orminimization) of metal foil current collectors, and 4) potential costsavings due to simpler manufacturing.

Anode electrodes currently used in the rechargeable lithium-ion cellstypically have a specific capacity of approximately 200 milliamp hoursper gram (including the metal foil current collector, conductiveadditives, and binder material). Graphite, the active material used inmost lithium ion battery anodes, has a theoretical energy density of 372milliamp hours per gram (mAh/g). In comparison, silicon has a hightheoretical capacity of 4200 mAh/g. In order to increase volumetric andgravimetric energy density of lithium-ion batteries, silicon may be usedas the active material for the cathode or anode. Several types ofsilicon materials, e.g., silicon nanopowders, silicon nanofibers, poroussilicon, and ball-milled silicon, have also been reported as viablecandidates as active materials for the negative or positive electrode.Small particle sizes (for example, sizes in the nanometer range)generally can increase cycle life performance. They also can displayvery high irreversible capacity. However, small particle sizes also canresult in very low volumetric energy density (for example, for theoverall cell stack) due to the difficulty of packing the activematerial. Larger particle sizes, (for example, sizes in the micrometeror micron range) generally can result in higher density anode material.However, the expansion of the silicon active material can result in poorcycle life due to particle cracking. For example, silicon can swell inexcess of 300% upon lithium insertion. Because of this expansion, anodesincluding silicon should be allowed to expand while maintainingelectrical contact between the silicon particles.

As described herein and in U.S. patent application Ser. Nos. 13/008,800and 13/601,976, entitled “Composite Materials for ElectrochemicalStorage” and “Silicon Particles for Battery Electrodes,” respectively,certain embodiments utilize a method of creating monolithic,self-supported anodes using a carbonized polymer. Because the polymer isconverted into an electrically conductive and electrochemically activematrix, the resulting electrode is conductive enough that a metal foilor mesh current collector can be omitted or minimized. The convertedpolymer also acts as an expansion buffer for silicon particles duringcycling so that a high cycle life can be achieved. In certainembodiments, the resulting electrode is an electrode that is comprisedsubstantially of active material. In further embodiments, the resultingelectrode is substantially active material. The electrodes can have ahigh energy density of between about 500 mAh/g to about 1200 mAh/g thatcan be due to, for example, 1) the use of silicon, 2) elimination orsubstantial reduction of metal current collectors, and 3) beingcomprised entirely or substantially entirely of active material.

The composite materials described herein can be used as an anode in mostconventional lithium ion batteries; they may also be used as the cathodein some electrochemical couples with additional additives. The compositematerials can also be used in either secondary batteries (e.g.,rechargeable) or primary batteries (e.g., non-rechargeable). In certainembodiments, the composite materials are self-supported structures. Infurther embodiments, the composite materials are self-supportedmonolithic structures. For example, a collector may be included in theelectrode comprised of the composite material. In certain embodiments,the composite material can be used to form carbon structures discussedin U.S. patent application No. 12/838,368 entitled “Carbon ElectrodeStructures for Batteries,” the entirety of which is hereby incorporatedby reference. Furthermore, the composite materials described herein canbe, for example, silicon composite materials, carbon compositematerials, and/or silicon-carbon composite materials. Certainembodiments described herein can further include composite materialsincluding micron-sized silicon particles. For example, in someembodiments, the micron-sized silicon particles have nanometer-sizedfeatures on the surface. Silicon particles with such a geometry may havethe benefits of both micron-sized silicon particles (e.g., high energydensity) and nanometer-sized silicon particles (e.g., good cyclingbehavior). As used herein, the term “silicon particles” in generalinclude micron-sized silicon particles with or without nanometer-sizedfeatures.

FIG. 1 illustrates one embodiment of a method of forming a compositematerial 100. For example, the method of forming a composite materialcan include forming a mixture including a precursor, block 101. Themethod can further include pyrolysing the precursor to convert theprecursor to a carbon phase. The precursor mixture may include carbonadditives such as graphite active material, chopped or milled carbonfiber, carbon nanofibers, carbon nanotubes, and/or other carbons. Afterthe precursor is pyrolyzed, the resulting carbon material can be aself-supporting monolithic structure. In certain embodiments, one ormore materials are added to the mixture to form a composite material.For example, silicon particles can be added to the mixture. Thecarbonized precursor results in an electrochemically active structurethat holds the composite material together. For example, the carbonizedprecursor can be a substantially continuous phase. The siliconparticles, including micron-sized silicon particles with or withoutnanometer-sized features, may be distributed throughout the compositematerial. Advantageously, the carbonized precursor can be a structuralmaterial as well as an electro-chemically active and electricallyconductive material. In certain embodiments, material particles added tothe mixture are homogenously or substantially homogeneously distributedthroughout the composite material to form a homogeneous or substantiallyhomogeneous composite.

The mixture can include a variety of different components. The mixturecan include one or more precursors. In certain embodiments, theprecursor is a hydrocarbon compound. For example, the precursor caninclude polyamic acid, polyimide, etc. Other precursors can includephenolic resins, epoxy resins, and/or other polymers. The mixture canfurther include a solvent. For example, the solvent can beN-methyl-pyrrolidone (NMP). Other possible solvents include acetone,diethyl ether, gamma butyrolactone, isopropanol, dimethyl carbonate,ethyl carbonate, dimethoxyethane, ethanol, methanol, etc. Examples ofprecursor and solvent solutions include PI-2611 (HD Microsystems),PI-5878G (HD Microsystems) and VTEC PI-1388 (RBI, Inc.). PI-2611 iscomprised of >60% n-methyl-2-pyrrolidone and 10-30%s-biphenyldianhydride/p-phenylenediamine. PI-5878G is comprised of >60%n-methylpyrrolidone, 10-30% polyamic acid of pyromelliticdianhydride/oxydianiline, 10-30% aromatic hydrocarbon (petroleumdistillate) including 5-10% 1,2,4-trimethylbenzene. In certainembodiments, the amount of precursor in the solvent is about 10 wt. % toabout 30 wt. %. Additional materials can also be included in themixture. For example, as previously discussed, silicon particles orcarbon particles including graphite active material, chopped or milledcarbon fiber, carbon nanofibers, carbon nanotubes, and other conductivecarbons can be added to the mixture. In addition, the mixture can bemixed to homogenize the mixture.

In certain embodiments, the mixture is cast on a substrate, block 102 inFIG. 1. In some embodiments, casting includes using a gap extrusion or ablade casting technique. The blade casting technique can includeapplying a coating to the substrate by using a flat surface (e.g.,blade) which is controlled to be a certain distance above the substrate.A liquid or slurry can be applied to the substrate, and the blade can bepassed over the liquid to spread the liquid over the substrate. Thethickness of the coating can be controlled by the gap between the bladeand the substrate since the liquid passes through the gap. As the liquidpasses through the gap, excess liquid can also be scraped off. Forexample, the mixture can be cast on a substrate comprising a polymersheet, a polymer roll, and/or foils or rolls made of glass or metal. Themixture can then be dried to remove the solvent, block 103. For example,a polyamic acid and NMP solution can be dried at about 110° C. for about2 hours to remove the NMP solution. The dried mixture can then beremoved from the substrate. For example, an aluminum substrate can beetched away with HCl. Alternatively, the dried mixture can be removedfrom the substrate by peeling or otherwise mechanically removing thedried mixture from the substrate. In some embodiments, the substratecomprises polyethylene terephthalate (PET), including for exampleMylar®. In certain embodiments, the dried mixture is a film or sheet. Insome embodiments, the dried mixture is cured, block 104. A hot press canbe used to cure and to keep the dried mixture flat. For example, thedried mixture from a polyamic acid and NMP solution can be hot pressedat about 200° C. for about 8 to 16 hours. Alternatively, the entireprocess including casting and drying can be done as a roll-to-rollprocess using standard film-handling equipment. The dried mixture can berinsed to remove any solvents or etchants that may remain. For example,de-ionized (DI) water can be used to rinse the dried mixture. In certainembodiments, tape casting techniques can be used for the casting. Inother embodiments, there is no substrate for casting and the anode filmdoes not need to be removed from any substrate. The dried mixture may becut or mechanically sectioned into smaller pieces.

The mixture further goes through pyrolysis to convert the polymerprecursor to carbon, block 105. In certain embodiments, the mixture ispyrolysed in a reducing atmosphere. For example, an inert atmosphere, avacuum and/or flowing argon, nitrogen, or helium gas can be used. Insome embodiments, the mixture is heated to about 900° C. to about 1350°C. For example, polyimide formed from polyamic acid can be carbonized atabout 1175° C. for about one hour. In certain embodiments, the heat uprate and/or cool down rate of the mixture is about 10° C./min. A holdermay be used to keep the mixture in a particular geometry. The holder canbe graphite, metal, etc. In certain embodiments, the mixture is heldflat. After the mixture is pyrolysed, tabs can be attached to thepyrolysed material to form electrical contacts. For example, nickel,copper or alloys thereof can be used for the tabs.

In certain embodiments, one or more of the methods described herein canbe carried out in a continuous process. In certain embodiments, casting,drying, curing and pyrolysis can be performed in a continuous process.For example, the mixture can be coated onto a glass or metal cylinder.The mixture can be dried while rotating on the cylinder to create afilm. The film can be transferred as a roll or peeled and fed intoanother machine for further processing. Extrusion and other filmmanufacturing techniques known in industry could also be utilized priorto the pyrolysis step.

Pyrolysis of the precursor results in a carbon material (e.g., at leastone carbon phase). In certain embodiments, the carbon material is a hardcarbon. In some embodiments, the precursor is any material that can bepyrolysed to form a hard carbon. When the mixture includes one or moreadditional materials or phases in addition to the carbonized precursor,a composite material can be created. In particular, the mixture caninclude silicon particles, creating a silicon-carbon (e.g., at least onefirst phase comprising silicon and at least one second phase comprisingcarbon) or silicon-carbon-carbon (e.g., at least one first phasecomprising silicon, at least one second phase comprising carbon, and atleast one third phase comprising carbon) composite material. Siliconparticles can increase the specific lithium insertion capacity of thecomposite material. When silicon absorbs lithium ions, it experiences alarge volume increase on the order of 300+ volume percent which cancause electrode structural integrity issues. In addition to volumetricexpansion related problems, silicon is not inherently electricallyconductive, but becomes conductive when it is alloyed with lithium(e.g., lithiation). When silicon de-lithiates, the surface of thesilicon loses electrical conductivity. Furthermore, when siliconde-lithiates, the volume decreases which results in the possibility ofthe silicon particle losing contact with the matrix. The dramatic changein volume also results in mechanical failure of the silicon particlestructure, in turn, causing it to pulverize.

Pulverization and loss of electrical contact have made it a challenge touse silicon as an active material in lithium-ion batteries. A reductionin the initial size of the silicon particles can prevent furtherpulverization of the silicon powder as well as minimizing the loss ofsurface electrical conductivity. Furthermore, adding material to thecomposite that can elastically deform with the change in volume of thesilicon particles can ensure that electrical contact to the surface ofthe silicon is not lost. For example, the composite material can includecarbons such as graphite which contributes to the ability of thecomposite to absorb expansion and which is also capable of intercalatinglithium ions adding to the storage capacity of the electrode (e.g.,chemically active). Therefore, the composite material may include one ormore types of carbon phases.

In some embodiments, a largest dimension of the silicon particles can beless than about 40 μm, less than about 1 μm, between about 10 nm andabout 40 μm, between about 10 nm and about 1 μm, less than about 500 nm,less than about 100 nm, and about 100 nm. All, substantially all, or atleast some of the silicon particles may comprise the largest dimensiondescribed above. For example, an average or median largest dimension ofthe silicon particles can be less than about 40 μm, less than about 1μm, between about 10 nm and about 40 μm, between about 10 nm and about 1μm, less than about 500 nm, less than about 100 nm, and about 100 nm.The amount of silicon in the composite material can be greater than zeropercent by weight of the mixture and composite material. In certainembodiments, the mixture comprises an amount of silicon, the amountbeing within a range of from about 0% to about 90% by weight, includingfrom about 30% to about 80% by weight of the mixture. The amount ofsilicon in the composite material can be within a range of from about 0%to about 35% by weight, including from about 0% to about 25% by weight,from about 10% to about 35% by weight, and about 20% by weight. Infurther certain embodiments, the amount of silicon in the mixture is atleast about 30% by weight. Additional embodiments of the amount ofsilicon in the composite material include more than about 50% by weight,between about 30% and about 80% by weight, between about 50% and about70% by weight, and between about 60% and about 80% by weight.Furthermore, the silicon particles may or may not be pure silicon. Forexample, the silicon particles may be substantially silicon or may be asilicon alloy. In one embodiment, the silicon alloy includes silicon asthe primary constituent along with one or more other elements.

As described herein, micron-sized silicon particles can provide goodvolumetric and gravimetric energy density combined with good cycle life.In certain embodiments, to obtain the benefits of both micron-sizedsilicon particles (e.g., high energy density) and nanometer-sizedsilicon particles (e.g., good cycle behavior), silicon particles canhave an average particle size in the micron range and a surfaceincluding nanometer-sized features. In some embodiments, the siliconparticles have an average particle size (e.g., average diameter oraverage largest dimension) between about 0.1 μm and about 30 μm orbetween about 0.1 μm and all values up to about 30 μm. For example, thesilicon particles can have an average particle size between about 0.5 μmand about 25 μm, between about 0.5 μm and about 20 μm, between about 0.5μm and about 15 μm, between about 0.5 μm and about 10 μm, between about0.5 μm and about 5 μm, between about 0.5 μm and about 2 μm, betweenabout 1 μm and about 20 μm, between about 1 μm and about 15 μm, betweenabout 1 μm and about 10 μm, between about 5 μm and about 20 μm, etc.Thus, the average particle size can be any value between about 0.1 μmand about 30 μm, e.g., 0.1 μm, 0.5 μm, 1 μm, 5 μm, 10 μm, 15 μm, 20 μm,25 μm, and 30 μm.

The nanometer-sized features can include an average feature size (e.g.,an average diameter or an average largest dimension) between about 1 nmand about 1 μm, between about 1 nm and about 750 nm, between about 1 nmand about 500 nm, between about 1 nm and about 250 nm, between about 1nm and about 100 nm, between about 10 nm and about 500 nm, between about10 nm and about 250 nm, between about 10 nm and about 100 nm, betweenabout 10 nm and about 75 nm, or between about 10 nm and about 50 nm. Thefeatures can include silicon.

The amount of carbon obtained from the precursor can be about 50 weightpercent from polyamic acid. In certain embodiments, the amount of carbonfrom the precursor in the composite material is about 10% to about 25%by weight. The carbon from the precursor can be hard carbon. Hard carboncan be a carbon that does not convert into graphite even with heating inexcess of 2800 degrees Celsius. Precursors that melt or flow duringpyrolysis convert into soft carbons and/or graphite with sufficienttemperature and/or pressure. Hard carbon may be selected since softcarbon precursors may flow and soft carbons and graphite aremechanically weaker than hard carbons. Other possible hard carbonprecursors can include phenolic resins, epoxy resins, and other polymersthat have a very high melting point or are crosslinked. In someembodiments, the amount of hard carbon in the composite material has avalue within a range of from about 10% to about 25% by weight, about 20%by weight, or more than about 50% by weight. In certain embodiments, thehard carbon phase is substantially amorphous. In other embodiments, thehard carbon phase is substantially crystalline. In further embodiments,the hard carbon phase includes amorphous and crystalline carbon. Thehard carbon phase can be a matrix phase in the composite material. Thehard carbon can also be embedded in the pores of the additives includingsilicon. The hard carbon may react with some of the additives to createsome materials at interfaces. For example, there may be a siliconcarbide layer between silicon particles and the hard carbon.

In certain embodiments, graphite particles are added to the mixture.Advantageously, graphite can be an electrochemically active material inthe battery as well as an elastic deformable material that can respondto volume change of the silicon particles. Graphite is the preferredactive anode material for certain classes of lithium-ion batteriescurrently on the market because it has a low irreversible capacity.Additionally, graphite is softer than hard carbon and can better absorbthe volume expansion of silicon additives. In certain embodiments, alargest dimension of the graphite particles is between about 0.5 micronsand about 20 microns. All, substantially all, or at least some of thegraphite particles may comprise the largest dimension described herein.In further embodiments, an average or median largest dimension of thegraphite particles is between about 0.5 microns and about 20 microns. Incertain embodiments, the mixture includes greater than 0% and less thanabout 80% by weight of graphite particles. In further embodiments, thecomposite material includes about 40% to about 75% by weight graphiteparticles.

In certain embodiments, conductive particles which may also beelectrochemically active are added to the mixture. Such particles canenable both a more electronically conductive composite as well as a moremechanically deformable composite capable of absorbing the largevolumetric change incurred during lithiation and de-lithiation. Incertain embodiments, a largest dimension of the conductive particles isbetween about 10 nanometers and about 7 millimeters. All, substantiallyall, or at least some of the conductive particles may comprise thelargest dimension described herein. In further embodiments, an averageor median largest dimension of the conductive particles is between about10 nm and about 7 millimeters. In certain embodiments, the mixtureincludes greater than zero and up to about 80% by weight conductiveparticles. In further embodiments, the composite material includes about45% to about 80% by weight conductive particles. The conductiveparticles can be conductive carbon including carbon blacks, carbonfibers, carbon nanofibers, carbon nanotubes, etc. Many carbons that areconsidered as conductive additives that are not electrochemically activebecome active once pyrolyzed in a polymer matrix. Alternatively, theconductive particles can be metals or alloys including copper, nickel,or stainless steel.

In certain embodiments, an electrode can include a composite materialdescribed herein. For example, a composite material can form aself-supported monolithic electrode. The pyrolysed carbon phase (e.g.,hard carbon phase) of the composite material can hold together andstructurally support the particles that were added to the mixture. Incertain embodiments, the self-supported monolithic electrode does notinclude a separate collector layer and/or other supportive structures.In some embodiments, the composite material and/or electrode does notinclude a polymer beyond trace amounts that remain after pyrolysis ofthe precursor. In further embodiments, the composite material and/orelectrode does not include a non-electrically conductive binder. Thecomposite material may also include porosity. For example, the porositycan be about 5% to about 40% by volume porosity.

The composite material may also be formed into a powder. For example,the composite material can be ground into a powder. The compositematerial powder can be used as an active material for an electrode. Forexample, the composite material powder can be deposited on a collectorin a manner similar to making a conventional electrode structure, asknown in the industry.

In certain embodiments, an electrode in a battery or electrochemicalcell can include a composite material, including composite material withthe silicon particles described herein. For example, the compositematerial can be used for the anode and/or cathode. In certainembodiments, the battery is a lithium ion battery. In furtherembodiments, the battery is a secondary battery, or in otherembodiments, the battery is a primary battery.

Furthermore, the full capacity of the composite material may not beutilized during use of the battery to improve life of the battery (e.g.,number charge and discharge cycles before the battery fails or theperformance of the battery decreases below a usability level). Forexample, a composite material with about 70% by weight siliconparticles, about 20% by weight carbon from a precursor, and about 10% byweight graphite may have a maximum gravimetric capacity of about 2000mAh/g, while the composite material may only be used up to a gravimetriccapacity of about 550 to about 850 mAh/g. Although, the maximumgravimetric capacity of the composite material may not be utilized,using the composite material at a lower capacity can still achieve ahigher capacity than certain lithium ion batteries. In certainembodiments, the composite material is used or only used at agravimetric capacity below about 70% of the composite material's maximumgravimetric capacity. For example, the composite material is not used ata gravimetric capacity above about 70% of the composite material'smaximum gravimetric capacity. In further embodiments, the compositematerial is used or only used at a gravimetric capacity below about 50%of the composite material's maximum gravimetric capacity or below about30% of the composite material's maximum gravimetric capacity.

Silicon Particles

Described herein are silicon particles for use in battery electrodes(e.g., anodes and cathodes). Anode electrodes currently used in therechargeable lithium-ion cells typically have a specific capacity ofapproximately 200 milliamp hours per gram (including the metal foilcurrent collector, conductive additives, and binder material). Graphite,the active material used in most lithium ion battery anodes, has atheoretical energy density of 372 milliamp hours per gram (mAh/g). Incomparison, silicon has a high theoretical capacity of 4200 mAh/g.Silicon, however, swells in excess of 300% upon lithium insertion.Because of this expansion, anodes including silicon should be able toexpand while allowing for the silicon to maintain electrical contactwith the silicon.

Some embodiments provide silicon particles that can be used as anelectro-chemically active material in an electrode. The electrode mayinclude binders and/or other electro-chemically active materials inaddition to the silicon particles. For example, the silicon particlesdescribed herein can be used as the silicon particles in the compositematerials described herein. In another example, an electrode can have anelectro-chemically active material layer on a current collector, and theelectro-chemically active material layer includes the silicon particles.The electro-chemically active material may also include one or moretypes of carbon.

Advantageously, the silicon particles described herein can improveperformance of electro-chemically active materials such as improvingcapacity and/or cycling performance. Furthermore, electro-chemicallyactive materials having such silicon particles may not significantlydegrade as a result of lithiation of the silicon particles.

In certain embodiments, the silicon particles have an average particlesize, for example an average diameter or an average largest dimension,between about 10 nm and about 40 μm. Further embodiments include averageparticle sizes of between about 1 μm and about 15 μm, between about 10nm and about 1 μm, and between about 100 nm and about 10 μm. Siliconparticles of various sizes can be separated by various methods such asby air classification, sieving or other screening methods. For example,a mesh size of 325 can be used separate particles that have a particlesize less than about 44 μm from particles that have a particle sizegreater than about 44 μm.

Furthermore, the silicon particles may have a distribution of particlesizes. For example, at least about 90% of the particles may haveparticle size, for example a diameter or a largest dimension, betweenabout 10 nm and about 40 μm, between about 1 μm and about 15 μm, betweenabout 10 nm and about 1 μm, and/or larger than 200 nm.

In some embodiments, the silicon particles may have an average surfacearea per unit mass of between about 1 to about 100 m²/g, about 1 toabout 80 m²/g, about 1 to about 60 m²/g, about 1 to about 50 m²/g, about1 to about 30 m²/g, about 1 to about 10 m²/g, about 1 to about 5 m²/g,about 2 to about 4 m²/g, or less than about 5 m²/g.

In certain embodiments, the silicon particles are at least partiallycrystalline, substantially crystalline, and/or fully crystalline.Furthermore, the silicon particles may be substantially pure silicon.

Compared with the silicon particles used in conventional electrodes, thesilicon particles described herein generally have a larger averageparticle size. In some embodiments, the average surface area of thesilicon particles described herein is generally smaller. Without beingbound to any particular theory, the lower surface area of the siliconparticles described herein may contribute to the enhanced performance ofelectrochemical cells. Typical lithium ion type rechargeable batteryanodes would contain nano-sized silicon particles. In an effort tofurther increase the capacity of the cell, smaller silicon particles(such as those in nano-size ranges) are being used for making theelectrode active materials. In some cases, the silicon particles aremilled to reduce the size of the particles. Sometimes the milling mayresult in roughened or scratched particle surface, which also increasesthe surface area. However, the increased surface area of siliconparticles may actually contribute to increased degradation ofelectrolytes, which lead to increased irreversible capacity loss. FIGS.2A and 2B are SEM micrographs of an example embodiment of siliconparticles milled-down from larger silicon particles. As shown in thefigures, certain embodiments may have a roughened surface.

As described herein, certain embodiments include silicon particles withsurface roughness in nanometer-sized ranges, e.g., micron-sized siliconparticles with nanometer-sized features on the surface. FIGS. 2C and 2Dare SEM micrographs of an example embodiment of such silicon particles.Various such silicon particles can have an average particle size (e.g.,an average diameter or an average largest dimension) in the micron range(e.g., as described herein, between about 0.1 μm and about 30 μm) and asurface including nanometer-sized features (e.g., as described herein,between about 1 nm and about 1 μm, between about 1 nm and about 750 nm,between about 1 nm and about 500 nm, between about 1 nm and about 250nm, between about 1 nm and about 100 nm, between about 10 nm and about500 nm, between about 10 nm and about 250 nm, between about 10 nm andabout 100 nm, between about 10 nm and about 75 nm, or between about 10nm and about 50 nm). The features can include silicon.

Compared to the example embodiment shown in FIGS. 2A and 2B, siliconparticles with a combined micron/nanometer-sized geometry (e.g., FIGS.2C and 2D) can have a higher surface area than milled-down particles.Thus, the silicon particles to be used can be determined by the desiredapplication and specifications.

Even though certain embodiments of silicon particles havenanometer-sized features on the surface, the total surface area of theparticles can be more similar to micron-sized particles than tonanometer-sized particles. For example, micron-sized silicon particles(e.g., silicon milled-down from large particles) typically have anaverage surface area per unit mass of over about 0.5 m²/g and less thanabout 2 m²/g (for example, using Brunauer Emmet Teller (BET) particlesurface area measurements), while nanometer-sized silicon particlestypically have an average surface area per unit mass of above about 100m²/g and less than about 500 m²/g. Certain embodiments described hereincan have an average surface area per unit mass between about 1 m²/g andabout 30 m²/g, between about 1 m²/g and about 25 m²/g, between about 1m²/g and about 20 m²/g, between about 1 m²/g and about 10 m²/g, betweenabout 2 m²/g and about 30 m²/g, between about 2 m²/g and about 25 m²/g,between about 2 m²/g and about 20 m²/g, between about 2 m²/g and about10 m²/g, between about 3 m²/g and about 30 m²/g, between about 3 m²/gand about 25 m²/g, between about 3 m²/g and about 20 m²/g, between about3 m²/g and about 10 m²/g (e.g., between about 3 m²/g and about 6 m²/g),between about 5 m²/g and about 30 m²/g, between about 5 m²/g and about25 m²/g, between about 5 m²/g and about 20 m²/g, between about 5 m²/gand about 15 m²/g, or between about 5 m²/g and about 10 m²/g.

Various examples of micron-sized silicon particles with nanometer-sizedfeatures can be used to form certain embodiments of composite materialsas described herein. For example, FIG. 3 illustrates an example method200 of forming certain embodiments of the composite material. The method200 includes providing a plurality of silicon particles (for example,silicon particles having an average particle size between about 0.1 μmand about 30 μm and a surface including nanometer-sized features), block210. The method 200 further includes forming a mixture that includes aprecursor and the plurality of silicon particles, block 220. The method200 further includes pyrolysing the precursor, block 230, to convert theprecursor into one or more types of carbon phases to form the compositematerial.

With respect to block 210 of method 200, silicon with thecharacteristics described herein can be synthesized as a product orbyproduct of a Fluidized Bed Reactor (FBR) process. For example, in theFBR process, useful material can be grown on seed silicon material.Typically, particles can be removed by gravity from the reactor. Somefine particulate silicon material can exit the reactor from the top ofthe reactor or can be deposited on the walls of the reactor. Thematerial that exits the top of the reactor or is deposited on the wallsof the reactor (e.g., byproduct material) can have nanoscale features ona microscale particle. In some such processes, a gas (e.g., a nitrogencarrier gas) can be passed through the silicon material. For example,the silicon material can be a plurality of granular silicon. The gas canbe passed through the silicon material at high enough velocities tosuspend the solid silicon material and make it behave as a fluid. Theprocess can be performed under an inert atmosphere, e.g., under nitrogenor argon. In some embodiments, silane gas can also be used, for example,to allow for metal silicon growth on the surface of the siliconparticles. The growth process from a gas phase can give the siliconparticles the unique surface characteristics, e.g., nanometer-sizedfeatures. Since silicon usually cleaves in a smooth shape, e.g., likeglass, certain embodiments of silicon particles formed using the FBRprocess can advantageously acquire small features, e.g., innanometer-sized ranges, that may not be as easily achievable in someembodiments of silicon particles formed by milling from larger siliconparticles.

In addition, since the FBR process can be under an inert atmosphere,very high purity particles (for example, higher than 99.9999% purity)can be achieved. In some embodiments, purity of between about 99.9999%and about 99.999999% can be achieved. In some embodiments, the FBRprocess can be similar to that used in the production of solar-gradepolysilicon while using 85% less energy than the traditional Siemensmethod, where polysilicon can be formed as trichlorosilane decomposesand deposits additional silicon material on high-purity silicon rods at1150° C. Because nanometer-sized silicon particles have been shown toincrease cycle life performance in electrochemical cells, micron-sizedsilicon particles have not been contemplated for use as electrochemicalactive materials in electrochemical cells.

With respect to blocks 220 and 230 of method 200, forming a mixture thatincludes a precursor and the plurality of silicon particles, block 220,and pyrolysing the precursor, block 230, to convert the precursor intoone or more types of carbon phases to form the composite material can besimilar to blocks 101 and 105 respectively, of method 100 describedherein. In some embodiments, pyrolysing (e.g., at about 900° C. to about1350° C.) occurs at temperatures below the melting point of silicon(e.g., at about 1414° C.) without affecting the nanometer-sized featuresof the silicon particles.

In accordance with certain embodiments described herein, certainmicron-sized silicon particles with nanometer surface feature canachieve high energy density, and can be used in composite materialsand/or electrodes for use in electro-chemical cells to improveperformance during cell cycling.

EXAMPLES

The below example processes for anode fabrication generally includemixing components together, casting those components onto a removablesubstrate, drying, curing, removing the substrate, then pyrolysing theresulting samples. N-Methyl-2-pyrrolidone (NMP) was typically used as asolvent to modify the viscosity of any mixture and render it castableusing a doctor blade approach.

Example 1

In Example 1, a polyimide liquid precursor (PI 2611 from HD Microsystemscorp.), graphite particles (SLP30 from Timcal corp.), conductive carbonparticles (Super P from Timcal corp.), and silicon particles (from AlfaAesar corp.) were mixed together for 5 minutes using a Spex 8000Dmachine in the weight ratio of 200:55:5:20. The mixture was then castonto aluminum foil and allowed to dry in a 90° C. oven, to drive awaysolvents, e.g., NMP. This is followed by a curing step at 200° C. in ahot press, under negligible pressure, for at least 12 hours. Thealuminum foil backing was then removed by etching in a 12.5% HClsolution. The remaining film was then rinsed in DI water, dried and thenpyrolyzed around an hour at 1175° C. under argon flow. The processresulted in a composition of 15.8% of PI 2611 derived carbon, 57.9% ofgraphite particles, 5.3% of carbon resulting from Super P, and 21.1% ofsilicon by weight.

The resulting electrodes were then tested in a pouch cell configurationagainst a lithium NMC oxide cathode. A typical cycling graph is shown inFIG. 4.

Example 2

In Example 2, silicon particles (from EVNANO Advanced Chemical MaterialsCo., Ltd.) were initially mixed with NMP using a Turbula mixer for aduration of one hour at a 1:9 weight ratio. Polyimide liquid precursor(PI 2611 from HD Microsystems corp.), graphite particles (SLP30 fromTimcal corp.), and carbon nanofibers (CNF from Pyrograf corp.) were thenadded to the Si:NMP mixture in the weight ratio of 200:55:5:200 andvortexed for around 2 minutes. The mixture was then cast onto aluminumfoil that was covered by a 21 μm thick copper mesh. The samples werethen allowed to dry in a 90° C. oven to drive away solvents, e.g., NMP.This was followed by a curing step at 200° C. in a hot press, undernegligible pressure, for at least 12 hours. The aluminum foil backingwas then removed by etching in a 12.5% HCl solution. The remaining filmwas then rinsed in DI water, dried and then pyrolyzed for around an hourat 1000° C. under argon. The process resulted in a composition of 15.8%of PI 2611 derived carbon, 57.9% of graphite particles, 5.3% of CNF, and21.1% of silicon by weight.

The resulting electrodes were then tested in a pouch cell configurationagainst a lithium NMC oxide cathode. A typical cycling graph is shown inFIG. 5.

Example 3

In Example 3, polyimide liquid precursor (PI 2611 from HD Microsystemscorp.), and 325 mesh silicon particles (from Alfa Aesar corp.) weremixed together using a Turbula mixer for a duration of 1 hour in theweight ratios of 40:1. The mixture was then cast onto aluminum foil andallowed to dry in a 90° C. oven to drive away solvents, e.g., NMP. Thiswas followed by a curing step at 200° C. in a hot press, undernegligible pressure, for at least 12 hours. The aluminum foil backingwas then removed by etching in a 12.5% HCl solution. The remaining filmwas then rinsed in DI water, dried and then pyrolyzed around an hour at1175° C. under argon flow. The process resulted in a composition of 75%of PI 2611 derived carbon and 25% of silicon by weight.

The resulting electrodes were then tested in a pouch cell configurationagainst a lithium NMC Oxide cathode. A typical cycling graph is shown inFIG. 6.

Example 4

In Example 4, silicon microparticles (from Alfa Aesar corp.), polyimideliquid precursor (PI 2611 from HD Microsystems corp.), graphiteparticles (SLP30 from Timcal corp.), milled carbon fibers (from FibreGlast Developments corp.), carbon nanofibers (CNF from Pyrograf corp.),carbon nanotubes (from CNANO Technology Limited), conductive carbonparticles (Super P from Timcal corp.), conductive graphite particles(KS6 from Timca corp.) were mixed in the weight ratio of20:200:30:8:4:2:1:15 using a vortexer for 5 minutes. The mixture wasthen cast onto aluminum foil. The samples were then allowed to dry in a90° C. oven to drive away solvents, e.g., NMP. This was followed by acuring step at 200° C. in a hot press, under negligible pressure, for atleast 12 hours. The aluminum foil backing was then removed by etching ina 12.5% HCl solution. The remaining film was then rinsed in DI water,dried and then pyrolyzed for around an hour at 1175° C. under argon. Theprocess resulted in a composition similar to the original mixture butwith a PI 2611 derived carbon portion that was 7.5% the original weightof the polyimide precursor.

The resulting electrodes were then tested in a pouch cell configurationagainst a lithium NMC oxide cathode. A typical cycling graph is shown inFIG. 7.

Example 5

In Example 5, polyimide liquid precursor (PI 2611 from HD Microsystemscorp.), and silicon microparticles (from Alfa Aesar corp.) were mixedtogether using a Turbula mixer for a duration of 1 hours in the weightratio of 4:1. The mixture was then cast onto aluminum foil covered witha carbon veil (from Fibre Glast Developments Corporation) and allowed todry in a 90° C. oven to drive away solvents, e.g., NMP. This wasfollowed by a curing step at 200° C. in a hot press, under negligiblepressure, for at least 12 hours. The aluminum foil backing was thenremoved by etching in a 12.5% HCl solution. The remaining film was thenrinsed in DI water, dried and then pyrolyzed around an hour at 1175° C.under argon flow. The process resulted in a composition of approximately23% of PI 2611 derived carbon, 76% of silicon by weight, and the weightof the veil being negligible.

The resulting electrodes were then tested in a pouch cell configurationagainst a lithium nickel manganese cobalt oxide (NMC) cathode. A typicalcycling graph is shown in FIG. 8.

Example 6

In Example 6, polyimide liquid precursor (PI 2611 from HD Microsystemscorp.), graphite particles (SLP30 from Timcal corp.), and siliconmicroparticles (from Alfa Aesar corp.) were mixed together for 5 minutesusing a Spex 8000D machine in the weight ratio of 200:10:70. The mixturewas then cast onto aluminum foil and allowed to dry in a 90° C. oven, todrive away solvents (e.g., NMP). The dried mixture was cured at 200° C.in a hot press, under negligible pressure, for at least 12 hours. Thealuminum foil backing was then removed by etching in a 12.5% HClsolution. The remaining film was then rinsed in DI water, dried and thenpyrolyzed at 1175° C. for about one hour under argon flow. The processresulted in a composition of 15.8% of PI 2611 derived carbon, 10.5% ofgraphite particles, 73.7% of silicon by weight.

The resulting electrodes were then tested in a pouch cell configurationagainst a lithium NMC oxide cathode. The anodes where charged to 600mAh/g each cycle and the discharge capacity per cycle was recorded. Atypical cycling graph is shown in FIG. 9.

Example 7

In Example 7, PVDF and silicon particles (from EVNANO Advanced ChemicalMaterials Co), conductive carbon particles (Super P from Timcal corp.),conductive graphite particles (KS6 from Timcal corp.), graphiteparticles (SLP30 from Timcal corp.) and NMP were mixed in the weightratio of 5:20:1:4:70:95. The mixture was then cast on a copper substrateand then placed in a 90° C. oven to drive away solvents, e.g., NMP. Theresulting electrodes were then tested in a pouch cell configurationagainst a lithium NMC Oxide cathode. A typical cycling graph is shown inFIG. 10.

Example 8

Multiple experiments were conducted in order to find the effects ofvarying the percentage of polyimide derive carbon (e.g. 2611c) whiledecreasing the percentage of graphite particles (SLP30 from Timcalcorp.) and keeping the percentage of silicon microparticles (from AlfaAesar corp.) at 20 wt. %.

As shown in FIGS. 11A and 11B, the results show that more graphite andless 2611c was beneficial to cell performance by increasing the specificcapacity while decreasing the irreversible capacity. Minimizing 2611cadversely affected the strength of the resultant anode so a value closeto 20 wt. % can be preferable as a compromise in one embodiment.

Example 9

Similar to example 8, if 2611c is kept at 20 wt. % and Si percentage isincreased at the expense of graphite particles, the first cycledischarge capacity of the resulting electrode is increased. FIG. 12shows that a higher silicon content can make a better performing anode.

Example 10

When 1 mil thick sheets of polyimide are pyrolized and tested inaccordance with the procedure in Example 1. The reversible capacity andirreversible capacity were plotted as a function of the pyrolysistemperature. FIG. 13 indicates that, in one embodiment, it is preferableto pyrolyze polyimide sheets (Upilex by UBE corp) at around 1175° C.

ADDITIONAL EXAMPLES

FIG. 14 is a photograph of a 4.3 cm×4.3 cm composite anode film withouta metal foil support layer. The composite anode film has a thickness ofabout 30 microns and has a composition of about 15.8% of PI 2611 derivedcarbon, about 10.5% of graphite particles, and about 73.7% of silicon byweight.

FIGS. 15-20 are scanning electron microscope (SEM) micrographs of acomposite anode film. The compositions of the composite anode film wereabout 15.8% of PI 2611 derived carbon, about 10.5% of graphiteparticles, and about 73.7% of silicon by weight.

FIGS. 15 and 16 show before being cycled (the out-of-focus portion is abottom portion of the anode and the portion that is in focus is acleaved edge of the composite film). FIGS. 17, 18, and 19 are SEMmicrographs of a composite anode film after being cycled 10 cycles, 10cycles, and 300 cycles, respectively. The SEM micrographs show thatthere is not any significant pulverization of the silicon and that theanodes do not have an excessive layer of solid electrolyteinterface/interphase (SEI) built on top of them after cycling. FIG. 20are SEM micrographs of cross-sections of composite anode films.

Described below are measured properties of example silicon particles.These examples are discussed for illustrative purposes and should not beconstrued to limit the scope of the disclosed embodiments.

FIG. 21 is an x-ray powder diffraction (XRD) graph of the sample siliconparticles. The XRD graph suggests that the sample silicon particles weresubstantially crystalline or polycrystalline in nature.

FIGS. 22-25 are scanning electron microscope (SEM) micrographs of thesample silicon particles. Although the SEM micrographs appear to showthat the silicon particles may have an average particle size greaterthan the measured average particle size of about 300 nm, without beingbound by theory, the particles are believed to have conglomeratedtogether to appear to be larger particles.

FIG. 26 is a chemical analysis of the sample silicon particles. Thechemical analysis suggests that the silicon particles were substantiallypure silicon.

FIGS. 27A and 27B are example particle size histograms of twomicron-sized silicon particles with nanometer-sized features. Theparticles were prepared from a FBR process. Example silicon particlescan have a particle size distribution. For example, at least 90% of theparticles may have a particle size, for example, a diameter or a largestdimension, between about 5 μm and about 20 μm (e.g., between about 6 μmand about 19 μm). At least about 50% of the particles may have aparticle size between about 1 μm and about 10 μm (e.g., about 2 μm andabout 9 μm). Furthermore, at least about 10% of the particles may have aparticle size between about 0.5 μm and about 2 μm (e.g., about 0.9 μmand about 1.1 μm).

FIG. 28 is a plot of discharge capacity during cell cycling comparingtwo types of example silicon particles. The performance of four samplesof silicon particles (micron-sized particles with nanometer-sizedfeatures) prepared by the FBR process are compared with five samples ofsilicon particles prepared by milling-down larger silicon particles.Thus, certain embodiments of silicon particles with the combinedmicron/nanometer geometry (e.g., prepared by the FBR process) can haveenhanced performance over various other embodiments of silicon particles(e.g., micron-sized silicon particles prepared by milling down fromlarger particles). The type of silicon particles to use can be tailoredfor the intended or desired application and specifications.

Various embodiments have been described above. Although the inventionhas been described with reference to these specific embodiments, thedescriptions are intended to be illustrative and are not intended to belimiting. Various modifications and applications may occur to thoseskilled in the art without departing from the true spirit and scope ofthe invention as defined in the appended claims.

What is claimed is:
 1. A method of forming a composite material, the method comprising: providing a mixture comprising: polyimide or a polyimide precursor; silicon particles; and graphite particles; and pyrolysing the mixture to convert the polyimide or the polyimide precursor into one or more carbon phases to form the composite material such that: the one or more carbon phases comprises hard carbon that is 10% to 25% by weight of the composite material and holds together the composite material, and the silicon particles are between 50% and 90% by weight of the composite material distributed throughout the one or more carbon phases.
 2. The method of claim 1, further comprising: casting the mixture on a substrate; drying the mixture; removing the dried mixture from the substrate; and placing the dried mixture in a hot press.
 3. The method of claim 1, further comprising forming a battery electrode from the composite material.
 4. The method of claim 1, wherein providing the mixture comprises providing silicon particles having an average largest dimension of 10 nm to 40 μm.
 5. The method of claim 1, wherein providing the mixture comprises providing conductive particles in the mixture.
 6. The method of claim 1, wherein providing the mixture comprises providing copper, nickel, or stainless steel particles in the mixture.
 7. The method of claim 1, wherein the composite material comprises more than 60% by weight silicon particles.
 8. The method of claim 1, wherein the composite material comprises 60% to 80% by weight silicon particles.
 9. The method of claim 1, wherein the composite material comprises 70% to 80% by weight silicon particles.
 10. The method of claim 1, wherein the composite material comprises 5% to 15% by weight graphite particles.
 11. The method of claim 10, wherein the composite material comprises 10.5% by weight graphite particles.
 12. The method of claim 1, wherein the composite material is electrochemically active.
 13. The method of claim 1, wherein at least one of the carbon phases is electrochemically active and electrically conductive.
 14. The method of claim 1, wherein at least one of the carbon phases is a continuous phase.
 15. A method of forming a battery cell, the method comprising: forming an anode of the battery cell, the anode comprising silicon particles and a composite material, wherein the forming comprises: providing a mixture comprising: polyimide or a polyimide precursor; silicon particles; and graphite particles; and pyrolysing the mixture to convert the polyimide or the polyimide precursor into one or more carbon phases to form the composite material such that: the one or more carbon phases comprises hard carbon that is 10% to 25% by weight of the composite material and holds together the composite material, and the silicon particles are between 50% and 90% by weight of the composite material distributed throughout the one or more carbon phases; and separating the anode from a cathode of the battery cell with a separator and electrolyte of the battery cell.
 16. The method of claim 15, wherein forming the anode further comprises: casting the mixture on a substrate; drying the mixture; removing the dried mixture from the substrate; and placing the dried mixture in a hot press.
 17. The method of claim 15, wherein providing the mixture comprises providing silicon particles having an average largest dimension of 10 nm to 40 μm.
 18. The method of claim 15, wherein providing the mixture comprises providing conductive particles in the mixture.
 19. The method of claim 15, wherein providing the mixture comprises providing copper, nickel, or stainless steel particles in the mixture.
 20. The method of claim 15, wherein the composite material comprises more than 60% by weight silicon particles.
 21. The method of claim 15, wherein the composite material comprises 60% to 80% by weight silicon particles.
 22. The method of claim 15, wherein the composite material comprises 70% to 80% by weight silicon particles.
 23. The method of claim 15, wherein the composite material comprises 5% to 15% by weight graphite particles.
 24. The method of claim 23, wherein the composite material comprises 10.5% by weight graphite particles.
 25. The method of claim 15, wherein the composite material is electrochemically active.
 26. The method of claim 15, wherein at least one of the carbon phases is electrochemically active and electrically conductive.
 27. The method of claim 15, wherein at least one of the carbon phases is a continuous phase. 